Process of producing improved wetting, sudsing, and detergent agents



Patented Feb. 22,1944

PROCESS OF PRODUCING WROVEB WETTING, AGENTS SUDSING, AND DETERGENT Nathaniel Beverley Tucker, Glendale; Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation Ohio No Drawing. Application December 12, 1941,

. Serial No. 422,684

15 Claims.

wherein R-CO is an acyl radical having eight to twenty-two carbon atoms and R1 is an alkyleneor hydroxy alkylene' radical having two to four carbon atoms. Illustrative compounds are the sodiumsalt of the oleic acid ester'oi isethionic acid (CnHaaCO-OCsHt-SOsNd) and the sodium salt 01 the coconut oil fatty acid (lauric acid predominantly) ester of 1,2-dihydroxy propane 3-su1fonic acid (CnHza-CQOCHz-CHOH-CHn-OaNa) These salts possess wetting, sudsing and detergent power in hard water, and in accordance with my invention are produced by the condensation of a salt of a higher fatty acid withealower molecular weight halogen substituted alkyl sulfonate in the presence of certain amides or substituted amides as more fully hereinafter set forth. It is an object of my invention to provide an improved method for the preparation of the above detergents. It is a further object to provide a process for the preparationof the above detergents which; as directly prepared, are freer of products of side reactions, contain a higher proportion of the desired product, and which contain an enhancing agent for further improvement in sudsing' and detergent power. Other objects of my invention will be apparent from the following description.

'In my copending application Serial No. 387,- 985, filed April 10, 1941, now U; S. Patent 2,289,- 391 01 which this application is a continuationin-part, I have described and claimed a related process for producing compound of the abovev type in which the soap and halogen substituted sulionate are condensed in the presence of certain amides or substituted amides whereby the condensation reaction is facilitated and deficiencies 01 prior art methods of preparation, necessarily involving expensive purification after consensation, are obviated. In this process the eiiect of the amide or substituted amide is to promote the condensation by making the reaction mass fluid-and miscible at temperatures below 200 C. at about which temperature undesirable and harmful decomposition products are formed, as much as fifty to several hundred per cent based on the combined weight of the soap and halogen substituted sulfonate being employed, to obtain the best results. The amides or substituted amides may or may not be removed from the reaction mix depending on Whether or not the ance or consistency standpoint and whether or not it is beneficial to the periorm'ance of the detergent in aqueous solution. Thus in the process of this copending application I am concerned with the use\oi amides or substituted amides which are volatilizable and which therefore may be removed from the reaction product at a temperature below that at which harmful decomposition products are formed.

In the present case I am not concerned. with the selection of amides or substituted amides of suitable volatility but rather with those amides and substituted amides which not only promote the condensationbetweenthe soap and halogen substituted sulfonate but also act as enhancing agents for the sudsing and detergent power of the condensation product when allowed to remain admixed therewith. In addition the present case is concerned with the use of the amides and substituted amides in a range oi proportions within which both of the above effects are ob tamed.

The amides which I use in practicin my pres ent invention are those mono-amides formed from fatty acids having ten to fourteen carbon atoms and compounds selected from the group consisting of morpholine, ethanolamine, 1 amino 2,3 propane diol, ammonia and. primary and secondary amines of the formula HNR"R where R is allsyl and R is hydrogen. or alkyl, the

- 4 sum of the carbon atoms in and being less than 5.

In the preferred practice of 1x13; soap 1S-heated at elevated tom-oer lower molecular weight halogen subs rention the with t. e tutecl allsyl d5 sulfonate in the presence of an amount of the amide or substituted amide which sufficient to promote the reaction but which lo below that amount detrimental to the detergent properties 01 the detergent formed when allowed to remain in admixture therewith. Such amounts are usually less than the optimum amount for condense tion but even so, considerabl benefit promo tion of the reaction-between the soap and the halogen substituted sulfonate is realized with the smaller amounts, and even though the amide or medium is objectionable from. an-odor', appearubstituted amide were removed after the comletion of the reaction the detergent product ould be better than that formed under comarable conditions without its presence.

After the reaction has reached substantial ompletion, as may be determined for example y titration of a sample of the mix for ionic alogen, the reaction mix without further reatment may be cooled and/or formed into my of a number of desirable forms for use in iunclering and other cleansing operations such 5 cakes, flakes, spray dried products. etc. Since 1e amides and substituted amides employed erein are also builders or enhancing agents for ie detergents in that they improve their cleans- 1g action, the products produced are far supeor to any thus far prepared, as far as I am ware.

My invention will be more clearly understood cm the following examples in which specific mditions of operation are set forth. However 1e invention is not limited to these specific conltions, as more particularly pointed out hereinfter.

Example 1.-- parts of dry sodium soap de- .ved from coconut oil are mixed with 40 parts i sodium monochlorhydrin sulfonate and 24 arts of lauroyl morphollne in a reaction vessel 'hich is not atteclged by the reactants, such. as

glass-lined vessel for example. The mixture is 30 eated with stirring at to C. for about hours, after which time the reaction between is soap and the monochlorhydrin sulfonate is ibstantially complete. The product, after coolig, is a white, stifi paste which dissolves in 'arm, hard water to give a clear solution posessing excellent detergent and sudsing power. Example 2.2 i parts sodium monochlorhydrin ulfonate, 23 parts dry sodium soap derived from oconut oil and 12 parts of butyl lauramide are lxed in a reaction vessel similar to that emloyed in Example 1 at C. for 1 hours, he product as prepared dissolves substantially ompletely in warm hard Water and possesses ery good detergent power.

The materials and conditions of operation sed in the above examples may be varied. For xample, while have shown the use of coconut il soap, other soaps such as oleic acid soap and naps of other fatty acids, individually and in dmixture, having eight to twenty-two carbon toms may be employed. Thus if desired, the :earates, palmitates, or myristates, or soaps rom any or" the natural occuring vegetable and nimal fats and oils may be used. Also, it should e noted that in addition to alkali metal soaps, llraline earth metal soaps such as calcium or :iagriesium soaps, or even some heavy metal caps may be used, provided the metal is such oat it readily combines with the halogen of the .alogen substituted sulfonate to produce a .eutral salt and provided that the metal does not orm an insoluble salt with the condensation roduct. I

In the examples I have shown the use of chloine substituted sulfonates because these deriva= ives are readily available or easily prepared. lowever, a sulfonate substituted with any other uita'ble halogen, such as bromine, may be emloyed with equal case without departing from 70 he spirit of the invention.

The kind of metal ion in the halogen subtituted sulfonate salt is relatively unimportant s long as the detergent agent, that is the conensation product, is Water soluble. Thus, for

. and halogen substituted sulfonate which may be example, the alkali metals, sodium and potassium, and the alkaline earth metals, calcium and magnesium, maybe employed since they to salts which are soluble in hard water.

The intermediate sulfonates, that is the halotassium beta methyl monochlorhyd'rin sulfonates,

sodium chlorethyl sulfonate, salts of chloro olefin sulfonic acids such as 2ichloromet'hyl propene sodium sulfonate, and others which will be readily apparent to those versed inthe art.

The amides and substituted amides employed in my invention do not take part in the reaction involved but promote the condensation, act as a flux in the formation of a fluid mixture of soap readily heated and stirred without danger of localized over-heating and in addition enhance the performance of the condensation product as a detergent in cleaning operations. Specific examples o1 amides and substituted amides which may be employed are the following:

Monobutyl amide of capric acid Dimethyl amide of myristic acid 7 CnHnCO-Nwmh Diethyl amide of lauric acid onne-co-N- (CzHe):

Methyl ethyl amide of lauric acid 7 CaHl CiiHiPC CH: Methyl propyl amide of ca'pric acid COHWCO'N 7 Although I have listed above only amides which are derived from specific fatty acids, it is to be understood that in the practice of the invention a mixture of amides derived-from a mixture of fatty acids consisting predominantly of fatty acids haying ten to fourteen carbon atoms such as may be ing the condensation'reaction is 140 to 150 0.,

but of course the condensation may be carried out at temperatures outside of these limits. For ex-- ample, some reaction is, evident at temperatures as low as 130 C. and such low temperatures may be fully sufilcient in some instances. Of course temperatures higher than 150 C. may also be employed, but temperatures substantially above 175 C. are usually unnecessary and may even be harmful since such high temperatures favor decomposition and the production of undesirable byproducts. v

The amount of amide or substituted amide which is employed in the present invention is that amount which is sufficiently large to promote'the reaction between the soap and the halogen substituted sulfonate but which is not sufficiently large to be detrimental to the performance of the condensation product in laundering or other cleansing operations. Ordinarily I employ an amount of reaction medium which is from about fifteen per cent to about fifty per cent of the combined weights of soap and halogen substituted sulfonate and these are my preferred quantities. However, the range is not definitely fixed andI may find it desirable to use from about ten per cent to about one hundred per cent of the combined weight of the reactants.

Having thus described my invention, what I claim and desire to secure by Letters Patent is:

1. In the process of producing an improved wetting, sudsing, and detergent agent of the general formula R'CO-ORrSOaMe where R-CO is the acyl radical of a fatty acid having eight to twenty-two'carbon atoms, R1 is a radical selected from the group consisting of a1- kylene and hydroxy alkylene radicals having two to four carbon atoms and Me is a metal forming a watei' soluble salt, the step which consists in condensing a metal salt of a fatty acid having eight to twenty-two carbon atoms with a halogen substituted sulfonate of the general formula X-Rr SOaMe where X is halogen' and'Ri and Me are as above indicated, in the presence of a mono-amide of the formula R-CO-A, wherein RC0 is the acyl radical of a fatty acid having ten to fourteen carbonv atoms and A is aradical selected from the group.

'70 B" being alkyl and R'" being selected from the group consisting ofhydrogen and alkyl, the sum of the number of carbon atoms in'R" and R' being less than 5. the amount of the mono-amide ting, sudsing and detergent agent substantially greater than one"hundred per cent based on the combined weights of the fatty acid salt and the halogen substituted sulfonate.

2. In the process of producing an improved wetof the general formula v r 'R-CO-ORi-SOsMe where R-CO is the acyl radical of a fatty acid having eight to twenty-two carbonatoms, R1 is a radical selected from the group consisting of alkylene and hydroxy alkylene radicals having two to four carbon atoms and Me is a metal forming a water soluble salt, the step which consists in condensing a metal salt. of a fatty acid having eight to twenty-two carbon atoms with a halogen substitutedsulfonate of the general formula- X-RrSOaMe where X is halogen and R1 and Me are as above indicated, in themresence of about fifteen per cent to about fifty per cent, based on the combined weight of the fatty acid salt and the halogen substituted sulfonate, of a mono-amide of the formula R-CO-A, wherein R-CO is the acyl radical .of a'fatty acid having ten to fourteen carbon atoms and A is a radical selected from the group consisting of R" being alkyl and R'" being selected from the group consisting of hydrogen and alkyl, the sum of the number of carbon atoms in R" and R being less than 5.

3. The process of cl...m 2 in which the radical R-CO represents a mixture of acyl radicals corresponding to a mixture of fatty acids consisting belns sufficient to promote the reaction but not 15 predominantly of fatty acids having fromfourteen carbon atoms per molecule.

' 4. The process of claim 2 in which the monoamide is derived from morphollne and a mixture of coconut oil fatty acids consisting predominantly of fatty acids having ten to fourteen carbon atoms per molecule.

5. The process of claim 2 in which the monoamide comprises essentially N -lauroyl morpholine. I

6. The process of claim 2 in which the halogen substituted sulfonate is monochlorhydrin' sodium sulfonate.

7. The process of claim 2 in which the fatty acid salt is sodium coconut oil soap, the halogen substituted sulfonate is monochlorhydrin sodium sulfonate, and the mono-amide comprises essentially N-lauroyl morpholi'ne.

8. Process of claim 2 in which the mono-amide is the amide of a mixture of coconut oil fatty acids consisting predominantly of fatty acids having ten to fourteen carbon atoms per molecule.

9. Process of claim 2 in which the mono-amide comprises essentially lauramide.

10. Process of claim 2 in which the fatty acid salt is sodium oleate and the halogen substituted sulfonate is monochlorhydrin sodium sulfonate.

11. Process of claim 2 in which the fatty acid ten to salt is sodium oleate, the halogen substituted sillfonate is monochlorhydrin sodium sulfonate, and the mono-amide comprises essentially lauramide. 12. Process of claim 2 in which the mono-amide molecule.

13. Process oi claim 2 in which the mono-amide comprises essentially the monoethanolamide 01 lauric acid.

14. The process of claim 2 in which the halogen substituted sulfonate is beta methyl monochlorhydrin sodium sulfonate.

15. Process of claim 2 in' which the fatty acid salt is sodium coconut oil soap, the halogen substituted sulfonate is beta methyl monochlorhydrin sodium sulionate, and the mono-amide comprises essentially the monoethanolamide of lauric acid.

NATHANIEL BEVERLEY TUCKER. 

